Textile materials and process for manufacturing them



United States Patent 3,216,780 TEXTILE MATERIALS AND PROCESS FOR MANUFACTURING THEM George Landells, Leeds, and Bernard Manogue, Baildon, near Shipley, Engiand, assignors to The Bradford Dyers Association Limited, Bradford, England, a corporation of the United Kingdom No Drawing. Filed Oct. 6, 1960, Ser. No. 60,777 Claims priority, application Great Britain, Oct. 8, 1959, 34,193/59 14 Claims. (Cl. 8-1163) This invention is concerned with the production of new and improved chemical modifications of cellulose and of cellulose derivatives which still retain reactive or replaceable hydrogen atoms.

The process of the invention is especially applicable to cellulose and cellulose derivatives in the fibrous state. In such application, when normally carried out, the process does not alter the essential fibrous character of the material.

As will become clear hereinafter the invention is applicable to cellulose in any convenient form, for example pulp, fibres, yarns, and woven or knitted fabrics, and sheet material such as non-woven fabrics, paper and regenerated cellulose films.

The process has the general elfect of reducing the solubility of the material in solvents which ordinarily dissolve it. It does not, however, reduce substantially, if at all, the swellability of the material in water, and it does not unduly weaken or embrittle the material. Amongst the specific eifects which the process may be used to bring about are increased wet crease recovery, increased dimensional stability, increased resistance to microbiological attack, with unimpaired or enhanced ability to receive dyeing and finishing operations.

The process of the invention for the treatment of material consisting wholly or in part of cellulose or of a cellulose derivative which still retains reactive or replaceable hydrogen atoms is characterised by subjecting the material to the action of an aqueous liquor which contains a methylolated nitrogen compound or compounds and an acid; the cellulose material which is swollen by the aqueous liquor is maintained in the swollen condition, i.e. prevented from drying out, while reaction takes place. Thereafter acidic matter is removed from the material and, after that, the material is dried. Removal of acidic matter is suitably efiected by neutralising and thorough rinsing in Water.

It will be observed that this process differs essentially from prior processes in which cellulose or a cellulose derivative is treated with an aqueous solution of an aldehydic compound or of a resin-forming aldehyde or methylolated condensation product, together with an acid or potentially acid substance, and then dried and heated to effect reaction.

In carrying out the invention the reaction liquor may be applied to the cellulosic material in a variety of convenient ways, which may depend upon the form of the cellulosic material. For example, the material may be steeped in a bath of the reaction liquor for the appropriate time for the reaction to have taken place. Alternatively, the reaction liquor may be circulated by mechanical means through a mass of pulp or fibres or yarn. Although, in the case of cellulosic material in the form of fabric or sheet, the process can conveniently be carried out by prolonged immersion thereof in a reaction bath,

3,216,780 Patented Nov. 9, 1965 it is more convenient simply to pad the material in the bath and then to batch it and allow it to stand for the required period of time, taking care, however, that it is not allowed to dry out during that period. With this object in mind, the batch may conveniently be wrapped in impervious material such as polyethylene sheeting. When the reaction times are reasonably short the treatment may be adapted to give a continuous process e.g. by skying the treated materials after impregnation .or by passing over a series of rollers before neutralisation and washing 01f. It is an essential feature of the invention that at all times during the reaction of the cellulosic material with the reactive chemicals the material must be in the wet swollen condition.

It is to be understood that when referring to cellulosic materials we include mixtures thereof with other materials, for example blended yarns or fabrics comprising other fibres such as wool, regenerated protein, nylon, polyethylene-terephthalate, cellulose triacetate or acrylics. The cellulosic material does not necessarily predominate in such mixtures.

The methylol compounds used in the process of the invention will normally be applied in solution in the aqueous acid.

It should be understood that the references herein to a methylol group apply equally to etherified methylol groups particularly methylated methylol groups. The word methylolated as used herein and in the claims is to be understood accordingly.

Polymethylol compounds and their ethers useful for the purpose of the invention include broadly those derived from amides, amidines and aminotriazines, which may be substituted, including cyclic compounds. Under amides we include ureas and urethanes, it being understood that these may also be substituted and may be cyclic or open chain.

Mixtures of methylol compounds may be used. Also reaction mixtures, resulting from processes for preparing the methylol compounds, which may have undergone partial or incipient reaction, may be used as such without isolating the essential methylol compound or compounds.

Particularly useful methylol compounds are heterocyclic compounds in which there are in the ring at least two nitrogen atoms to which methylol groups are directly attached respectively. The methylol groups in the polymethylol derivative may usually be external to the ring, but alternatively or in addition, the methylol group or groups may have the carbon atom thereof in the ring.

Examples of methylol derivatives of nitrogenous compounds which may be used in the process of the invention are:

Polymethylol compounds derived from ethylene urea and related compounds. Thus dimethylol ethylene urea, of the formula:

is effective.

Of special importance is the dimethylol derivative of dihydroxy ethylene urea of the formula:

3 Alternative names for this compound are 1,3-bis (hydroxy methyl) 4,5-dihydroxy imidazolidone, and dimethylol glyoxal monoureine.

Instead of using the said compound as such there may be used mixtures which may have been partially or incipiently reacted from the components glyoxal, urea and formaldehyde. Thus, glyoxal may be reacted first with urea under conditions which give essentially glyoxal monoureine which, without isolation, may thenbe methylolated by the addition of formaldehyde. The reaction mixture so formed may then be used for the process of the invention. Alternatively the three components glyoxal, urea and formaldehyde may be mixed together and allowed to react. Such a mixture is capable of producing methylolated glyoxal monoureine as well as methylolated urea derivatives. Whatever the nature of the reaction mixture it may be used for the process of the invention. A further alternative is firstly to react urea with formaldehyde to give methylol derivatives which may thereafter be reacted with glyoxal. A still further alternative which may sometimes be practicable and convenient is to add the components separately to the acid solution used for the treatment of the cellulosic material.

Alternative to glyoxal in the aforesaid reactions are pyruvic aldehyde and a-hydroxy adipaldehyde.

A further useful product related to ethylene urea is acetylene diurea. When methylolated this product, of the formula given below, gives technical effects when applied in conjunction with acid similar to those given by dimethylol dihydroxy, ethylene urea:

Other substituted ethylene ureas capable of giving suitable methylol compounds are alkyl' derivatives such as methyl ethylene urea:

CH3 CHrH' Hl r /NI-I oralkox-y derivatives, e.g. dimethoxy ethylene urea:

CH O 0011 H-- H H1 1 NE Instead of. ethylene urea the corresponding propylene urea derivatives may be used, the simplest of which is dimethylol propylene urea:

HOCH -N N-CH;OH

Another class ofcompounds capable of giving useful polymethylol derivatives are those based on triamino triazine or its related products ammeline and formo guanamine:

NH; ()H H Melamine Amrneline For-mo guanamine A further class of compounds capable of giving useful polymethylol derivatives are those based on the triazone (triazinone) ring. Such compounds are represented by the methyl-, ethyland hydroxyethyl-triazones, having the formulae respectively:

Polymethylol derivatives of other ring compounds containing nitrogen, e.g. those based on hydantoin or substituted hydantoins, e.g. monomethyl or dimethyl hydantoins, are useful. These ring compounds have the, formulae, respectively:

Polymethylol derivatives of uron and substituted urons are also useful.

Open chain compounds which may be used in the. process of the invention include the methylol derivatives of dicyandiamideand the methylol derivatives of adipamide.

Methylol derivatives of urea may also be used under. appropriate conditions in the process of the invention. The conditions must be chosen such that little, if any, precipitation occurs. Suitable conditions are small amounts of acid such that the pH is of the order 5-6, and long times and high temperatures. However strong acids may be employed with dimethylol urea if additions of various aldehydes are made e.g. formaldehyde, glyoxal, pyruvic aldehyde andu-hydroxy adipaldehyde, or alcohols, e.g; methanol, glycol and glycerol. It is presumed that. these additives react with the methylol compounds to prevent condensation.

Likewise, urea-formaldehyde mixtures of higher mole.- cular ratios of urea/formaldehyde e.g. 1:.4 are sufiiciently stable to add to concentrated acids.

In preparing the acidic solutions of reactants used for carrying out the process. ofv the invention mineral acids,- e.g. sulphuric acid, nitric acid, hydrochloric acid, or phosphoric acid are desirably used because there can be obtained with such acids relatively high hydrogen ion: concentrations and relatively low working temperatures can be employed. However, strong organic acids, e.g.

trichloracetic acid, may likewise be used and, further there may be used weaker organic acids although an elevated temperature will then normally be required for the treatment. acetic, tartaric, citric and oxalic acids.

The preferred acid when working-at room temperatures, i.e. about 20 C., is sulphuric acid, and at such temperatures the acid concentration is preferably 1 N to 10 Nand more preferably 4 N to 6 N acid strength and the material should be subjected to the reaction medium for some hours, normally at least 2 to 3 hours. However, some useful modification of the material subjected to the treatment may occur after 30 minutes. On the other hand the material may be subjected to the reaction medium for longer periods, e.g. 24 hours. It is convenient in most. cases to work at room temperature but if it is desired to. shorten thetime of treatment the temperature may be increased. Where however this would. cause undue damage to the cellulosic material it would alsobe TIGCES? sary to reduce the acid normality of the reaction medium, which may. then be less than 1 e.g. as low as 0.1 N or even 0.001 N.

For certain special effects with sulphuric acid it has been found that chemical. modification can occur at evenhigher acid normalities in the region of 20 N. Thus the reactants may be added to acid of parchmentising strength and used to produce new technical effects in fabrics processed according to our methods. In such treatments Examples of suitable weaker acids are formic however the times of reaction are of the order of one minute .or less. A guide to suitable times of treatment with solutions of different concentrations of sulphuric acid are given in the following table It is within the scope of the invention to add salts to the acid solution to modify the degree of swelling of the cellulose or the catalytic activity of the acid.

The invention is of special interest in that it provides simple and effective processes for the treatment of cellulosic materials in order to produce a number of improved technical effects. In textiles these include methods for the production of an outstandingly good wet crease recovery, and improved dimensional stability. Thus there may be produced fabrics which, when made up into the form of articles of clothing, can be washed and hung up to dry and then be fit to be worn without ironing. To obtain such smooth-drying fabrics steps should be taken to ensure that the fabric is free from creases whilst the reaction takes place because the fabric tends to set in the condition it is in at the time of the reaction. In some cases however the reaction may be coupled with a mechanical treatment e.g. glazing or pleating. Glazing may be carried out prior to the chemical reaction, but pleating is preferably effected in the wet state after the fabric has been impregnated with the reaction solution. In the case of modified cellulose containing reactive or replaceable hydrogen atoms e.g. cellulose diacetate the technical effect may be a higher softening temperature which is useful when the fabric is hot ironed.

It has been found, as regards dimensional stability, that in the case of fabrics composed wholly or mainly of normal regenerated cellulose there is obtained only a moderate degree of dimensional stability. The regenerated cellulose more particularly in mind is the filamentary material obtained by the regeneration of cellulose fibres from a solution of cellulose xanthate and the like.

It has been found however, that if such regenerated cellulose material is subjected to a pretreatment adapted to impart a degree of dimensional stability, the subsequent treatment with acid and methylolated nitrogen I compound will result in the material having a very much improved dimensional stability which is more than could be expected as a result of a summation of the effects which would be produced individually by the pretreatment and the subsequent treatment. In fact it appears that the combined treatments are synergistic in character.

The pretreatment may be, for example, a treatment with steam or superheated steam, or with a swelling agent preferably an alkaline substance such as caustic soda. A further type of pretreatment which involves incorporating resin in the material may be used.

The technical effects which may be obtained by the methods of the invention are not removed by repetitive washing as they are based on a chemical modification of the cellulose structure. It is an important feature of the present invention that fibres remain swellable in water and such treatments allow subsequent dyeing or finishing agents to be applied, particularly conventional resination treatments employing condensation resins of the aminoformaldehyde type by known techniques. stiffening agents, softening agents, water-repellents, fluorescent brighteners or other conventional finishing agents may be applied. Cellulosic fabrics treated according to the invention may be dyed with direct cotton dyes, vat dyes,

solubilised vat dyes, azoic dye combinations or with reactive dyes. Likewise fabrics or material may be printed by conventional techniques.

- It should be understood that the process of the invention may be applied to cellulosic fabrics and other cellulosic materials which have been previously subjected to certain normal finishing operations, e.g. resination with amino-formaldehyde condensates. Novel effects may be obtained by first impregnating fabrics in an aqueous dispersion of a cellulose ether and drying and then subjecting the impregnated fabric to the action of the reactant solutions according to our invention. The reactant appears to fix or modify the cellulose ether in addition to chemically modifying the substrate.

It will also be appreciated that finishing agents may be incorporated in the reaction liquors. Acid dispersible cellulose ethers may be fixed in this way.

If desired cellulose material which has been modified according to the invention may be subjected to an after treatment with a swelling agent or agents, for example treatment in caustic soda as in post-mercerisation may be carried out if desired.

Particularly useful preparations for the treatment of cellulosic material-s according to the invention contain between 5 and 25 parts by weight of dimethylol dihydroxy ethylene urea and between and 75 parts by weight of aqueous sulphuric acid of normality between 4 N and The following examples are given for the purpose of illustrating the present invention; in these examples where the word part or parts is used it means part or parts by weight.

Example 1 6.4 cc. concentrated sulphuric acid were added to cc. water and the mixture allowed to cool. 20 g. dimethylol ethylene urea were then dissolved in the mixture and the whole made up with water to 200 cc. Two specimens of mercerised cotton fabric were padded in the mixture at 60 C., wrapped in polyethylene sheet to' Example 2 18 g. trimethylol melamine were dissolved in 50 cc. water. 36 cc. concentrated sulphuric acid were separately added to 75 cc. water and allowed to cool. The two solutions were then thoroughly mixed and water was added to give a total volume of 200 cc. The acid normality of the solution was approximately 6 N. The impregnation solution so prepared was stable for at least 24 hours.

A plain weave dress cotton fabric Was padded in the prepared solution, squeezed, rolled free from creases and wrapped in polyethylene sheet to prevent evaporation. The batch was allowed to stand for 4 hours at 20 C. The treated fabric was then neutralised in sodium carbonate solution, well rinsed in Water, and allowed to dry. On washing, in comparison with the cotton fabric without treatment, a greatly improved wet crease resistance was obtained.

Example 3 An impregnationsolution was prepared as in Example 2 except that the trimethylol melamine was replaced by 20 g. dimethylol ethyl-s-triazinone. The bath could be allowed to stand for some days without loss of effectiveness.

Cotton fabric was impregnated as in Example 2 and allowed to stand for 4 hours. The fabric was neutralised in sodium carbonate solution, rinsed well in water, dried and wash tested as in Example 2.

Fibres taken from the treated fabric were insoluble in cuprammonium hydroxide and the treated fabric had improved wet crease resistance.

Example 4 12.5 g. dimethylol ethylene urea were dissolved in a mixture of 100 cc. concentrated hydrochloric acid and 100 cc. water and the whole made up to 250 cc. The solution so prepared was found to have an acid normality of 4.2 N.

A mercerised cotton fabric was impregnated in the prepared solution, squeezed, rolled free from creases, Wrapped in polyethylene sheeting and allowed to stand for 4 hours at 20 C. The fabric was then neutralised in sodium carbonate solution, rinsed well in water and allowed to dry.

A wash test on the treated fabric in comparison with a specimen of the same fabric before treatment showed that the wet crease resistance was much improved.

Example 5 5 g. dimethylol ethylene urea were dissolved in a mixture of 37.8 cc. concentrated nitric acid and 50 cc. water and the mixture adjusted to 100 cc. with water. The acid normality was found to be 5.72 N.

Mercerised cotton fabric was treated in this mixture by the same method as in Example 4. The treatment gave a similar improvement in wet crease resistance.

Example 6 18 cc. concentrated sulphuric acid were added to 50 cc. water and the mixture allowed to cool. g. dimethylol dihydroxyethyleneurea were added and the whole made up to 100 cc. with water. The acid normality was approximately 7.8 N. A specimen of mercerised cotton poplin was impregnated, squeezed and batched as in previous examples. After standing for 4 hours at 20 C. it was neutralised with dilute sodium carbonate solution, rinsed well with cold water and dried on a pin frame.

The fabric was found on washing to have greatly improved wet crease shedding properties.

A specimen of bleached mercerised 2-fold cotton yarn was impregnated in the same liquor, wound round a glass tube and left, protected from evaporation, for 4 hours at 20 C. andthen neutralized with sodium carbonate, rinsed well in water and dried. The yarn showed improved Wet crease recovery properties.

Example 7 A sample of mercerised cotton poplin was impregnated with a liquor prepared as in Example 6 with the substitution of 8.5 g. tetra-methylol acetylene diurea for the dimethylol dihydroxy ethylene urea, squeezed, batched and left for two hours at 20 C. After neutralization it was rinsedwell in water and dried on a pin frame.

On washing the fabric showed good wet crease shedding properties.

Example 8 Specimens of viscose rayon staple fibre shirting fabric were placed on a pin frame and immersed in aqueous solution of sodium hydroxide (5%) for 20 seconds at 20 C. They were then rinsed in cold water, neutralised, and dried. While maintained at original dimensions on the frame they were then immersed in solutions of sulphuric acid (5.5 N) containing respectively (1) ten parts dimethylol dihydroxy-ethylene urea (DM-OH-EU), (2) 8.6 parts dimethylol tetrahydro 5 ethyl-s-tn'azinone (DMT), (3) ten parts dimethylol ethylene urea (DMEU) for every 100 parts of solution. They were then rinsed, neutralized with a 1% aqueous solution of sodium carbonate, rinsed again in water whereby substantially all acid was removed and dried on a frame.

For purposes of comparison other specimens were similarly treated with the omission of the treatment with aqueous sodium hydroxide. Another specimen was similarly treated with the omission of the treatment with a dimethylol compound and sulphuric acid.

After washing for 5 minutes in a 0.2% aqueous soap solution and hanging to dry the specimens were found to have shrunk from their original dimensions by the percentages shown below.

Shrinkage (percent) Warp Weft Untreated 15.0 5. 25 Treated:

DM-OH-EU 5. 5 4. 0 DMT 9. 5 4. 0 DME U 9. 5 4. 0 Caustic Soda only 11.5 4. Caustic Soda followed by DM-OH U 3. 25 1. 5 Caustic Soda followed by DMT 6. 25 6. 25 Caustic Soda followed by DMEU 7. 0 4. 0

Fabrics treated with the methylol compounds also showed improved resistance to wet creasing.

Example 9 Specimens of viscose staple fibre fabric were treated in the same manner as in Example 8 except that they were stretched 5% warpwise during treatment with sodium hydroxide and during treatment with dimethylol compounds and finally dried at original dimensions.

After washing the specimens were found to have shrunk from their original dimensions by the percentages shown below.

Example 1.0

Viscose rayon staple fibre shirting fabric was treatedwith steam at 50 lbs./ sq. in. for five minutes. Specimens of steamed and unsteamed fabric were fixed in a pin frame and immersed for 2 hours at 20 C. in sulphuric acid (5.5 N) and containing ten parts dimethylol ethylene urea in parts of solution. They were then rinsed and dried as in Example 9 and tested for dimensional change on washing.

Shrinkage (percent) Warp I Weft Untreated 15.0 5. 25 Treated DMEU 10. 5 3. 0 Steamed only- 11. 0 1. 75 Steamed and treated DMEU; 6.0 2. 0

When specimens were similarly treated for 3 hours in a solution in which 8.6 parts dimethylol dihydroxyethylene urea was substituted for the dimethylol ethylene urea the results were as follows:

Shrinkage. (percent) Warp Weft Treated DM-OH-EU 5. 5 Steamed and treated DM-OH-EU 2. 75

Example 1] Specimens of steamed and unsteamed fabric were treated as in Example 10 except that the specimens were stretched warpwise during treatment with the dimethylol compounds then finally dried at original dimensions.

Dimensional changes on subsequent washing were as follows:

Fabrics treated with the methylol compounds also showed improved resistance to wet creasing.

Example 12 Two 20 -g. portions of a solution of dimethylol dihydroxy ethylene urea (50%) were diluted to 100 cc. and the pH of the solution adjusted to 3.1 and 6.6 respectively by addition of small amounts of sulphuric acid.

Specimens of plain unmercerised cotton fabric were padded in the respective solutions at 20 0., rolled onto a tube, wrapped in a polyethylene sheet to prevent evaporation and stored in an oven at 80 C. for 24 hours. When unrolled the cuttings were still wet with solution, and were neutralised in sodium carbonate solution, rinsed well in water and dried.

The treated specimens of fabric had improved wet crease recovery compared with untreated fabric.

Fibres from the treated fabric did not dissolve in cuprammonium hydroxide.

Example 13 treated fabric were insoluble in cuprammonium hydroxide solution.

Example 14 A reaction product of urea, formaldehyde, and glyoxal in the molecular proportions 1:2:1 was prepared by adding 156 cc. of glyoxal solution (37% w./v.) to 150 cc. formaldehyde solution (40% W./v.). The solution was adjusted to pH 8 by addition of sodium hydroxide solution; 60 g. of urea were then added. The mixture was stirred and allowed to stand for 48 hours. 20 g. of the reaction mixture were diluted with Water and added to 40 cc. 12 N sulphuric acid solution and the total volume made up to 100 cc. With water. Cuttings of mercerised cotton fabric Were padded in the solution, rolled on a tube, wrapped with polyethylene sheet to prevent evaporation, allowed to stand for 3 hours at 20 C. then neutralised in sodium carbonate solution, rinsed well in Water 1 and dried.

The treated fabric had improved wet crease shedding properties compared with the untreated fabric, and was insoluble in cuprammonium hydroxide.

I Specimens of treated fabric were buried in ground containing decaying vegetation together with untreated controls for 2 months. On removal the treated fabric was l 0 substantially unchanged and the untreated fabric was disintegrated.

A reaction product was prepared by the above method in which the 60 g. of urea was replaced by 78 g. thiourea. When applied to the fabric by the method indicated above this product also caused an improvement in the wet crease shedding properties of the fabric and the treated fabric was insoluble in cuprammonium hydroxide.

Example 15 60 g. urea were added to cc. formaldehyde solution (40% w./v.), 6 cc. ammonium hydroxide, specific gravity .880, were added and the mixture stirred. After 4 hours 162 cc. glyoxal solution (36% w./v.), which had been previously neutralised to pH 7 with sodium hydroxide solution, were added and the solution was allowed to stand for a further 16 hours. The free formaldehyde in the solution was found to be 2% 20 g. of the reaction mixture were added to 40 cc. 12 N sulphuric acid solution and the volume made up to 100 cc. with water. Specimens of cotton poplin fabric were padded and treated by the procedure of Example 14.

The treated fabric had good wet crease shedding properties and was insoluble in cuprammonium hydroxide solution.

Specimens of treated fabric were satisfactorily dyed respectively with:

A direct cotton dye Direct Brilliant Pink 3B (C.I.

Direct Red 11);

A vat dye Caledon Jade Green XN (C.I. Vat Green A solubilised vat dye Soledon Jade Green X (C.I. Solubilised Vat Green 1);

An azoic dye comprising Brenthol FR (C.I. Azoic Coupling Component 20) and Brentamine Fast Scarlet GG Salt (.C.I. Azoic Diazo Compound 3); and

A reactive dye Cibacron Turquoise Blue G (C1. Reactive Dye 7) -(Ciba Ltd.).

Example 16 100 g. urea were added to 250 cc. formaldehyde solution (40% w./v.), 10 cc. ammonium hydroxide solution (sp. gr. .880) were added and the mixture stirred. After 16 hours 165 cc. of water were added. The free formaldehyde of the solution was found to be less than 2%,

13.5 cc. glyoxal solution, concentration 37%, pH 1.3, were added to 38 g. of the urea-formaldehyde solution. A slight precipitate formed. The mixture was added to 40 cc. 13 N sulphuric acid solution when the precipitate dissolved and the volume made up to 100 cc. with water. The clear solution was stable for more than three days.

Specimens of cotton poplin fabric were padded in the solution and batched by the procedure of Example 14. After being neutralised in sodium carbonate solution, rinsed well in water and dried, the treated fabric was found to have excellent wet crease shedding properties. Fibres from the treated fabric were insoluble in cuprammonium hydroxide solution.

Example 17 hydrochloric acid without the dimethylol glyoxal monourein fused when ironed at 210-220 F.

The treated fabric was also found to be insoluble in acetone, whereas untreated fabric dissolved in acetone.

Example 18 20 g. of a solution of dimethylol dihydroxy ethylene urea (50% W./v.) were added to a dilute solution of,

1 1 acetic acid and the whole made up to 100 cc. with water. The solution had an acid normality of N/ 10.

Specimens of mercerised cotton poplin fabric were padded in the solution and treated by the procedure of Example 12'. The treated fabric had good wet crease shedding properties. Fibres from the treated fabric were insoluble in cuprammonium hydroxide solution. Similar properties were obtained when the N/lO acetic acid was replaced by N/ 10 solutions of oxalic acid, tartaric acid, citric acid, lactic acid or formic acid.

Example 19 6.4 cc. formaldehyde solution (40% w./v.) were added to 38 g. of an aqueous solution of dimethylol urea (27% w./w.) and this mixture was added to 40 cc. 13 N sulphuric acid, and the solution was made up to 100 cc. with water. The clear solution was stable for more than 24 hours.

Specimens of mercerised cotton poplin fabric were padded in this solution, and treated by the procedure of Example 14. The treated fabric had improved wet crease shedding properties when compared with untreated fabric and was insoluble in cuprammonium hydroxide solution.

As control experiments, specimens of the cotton poplin fabric were treated respectively in solutions which contained (a) 6.4 cc. formaldehyde solution per 100- cc. sulphuric acid .6 N), and (b) in a solution of sulphuric acid (5.6 N), but otherwise in a similar manner to the above specimens. Use of the acid alone did not give any improvement in wet crease shedding properties to the fabric- With formaldehyde and sulphuric acid only slight improvements in wet crease shedding were obtained.

Example 20 Specimens of mercerised cotton fabric were immersed at 20 C. in solution of sulphuric acid (20.2 N) containing g. dimethylol dihydroxy ethylene urea per 100 cc., for 1 minute. The specimens were removed, rinsed well with water, neutralised in sodium carbonate solution and finally rinsed with water. The treated fabric was parchmentised, the fibres were insoluble in cuprammonium hydroxide solution and the treated fabric showed improved wet crease shedding properties compared with fabric which had been parchmentised in the solution of sulphuric acid in the absence of dimethylol dihydroxy ethylene urea.

A specimen of pure cellulose paper (Whatman No. 1 filter paper) was treated similarly and was parchmentised showing an improved transparency, smoothness and less shrinkage than paper treated with the sulphuric acid solution alone.

Example 21 A reaction mixture of thiourea, formaldehyde and glyoxal in molecular ratio 121.5:1 was made by first adding 116 cc. formaldehyde solution (40% W./v.) to

76 g. thiourea and adjusting pH value to 8.5 with ammonium hydroxide. The mixture was warmed to 25 C. and reaction allowed to proceed exothermally. After 1 hour, 191 cc. glyoxal solution (30% w./v.)' previously neutralised with sodium hydroxide was added with stir ring. The solution was allowed to stand for 24 hours. 20 g. of the reaction mixture was diluted with water and added to 40 cc. 12 N sulphuric acid, and the volume was made to 100cc. with water. Specimens of mercerised cotton' poplin fabric were padded in the solution and the treatment completed by the procedure of Example 14. The treated fabric was found to have improved wet crease shedding properties when compared with the untreated fabric, and was insoluble in cuprammonium hydroxide solution.

Example 22 5 gallons commercial sulphuric acid solution (77% w./w.)- was added to 4- gallons water. The solution was cooled to 20 C. 40 lb. of a solution of dimethylol di hydroxy ethylene urea (45% w./w.) was diluted to 11 gallons with water and added to the diluted acid solution. A length of a twill Weave blended fabric, composition 78% cotton 22% wool, ends per inch 72, picks per inch 71, was padded in the solution, batched in polyethylene sheet to prevent evaporation and kept for 2 /2 hours at 18 C. The fabric was neutralised with sodium carbonate, rinsed well in water, and dried. The treated fabric showed improvements in resistance to creasing and in dimensional stability on washing, in a soap solution for 10 minutes at 60 C. in a household washing machine.

Shrinkage (percent) Washed once Washed 5 times Warp Weft Weft Warp Untreated -1. 0 6. 5 6. 5 Treated 0. 5 1. 2 1. 5

1 A negative sign signifies extension.

g. of a solution of dimethylol dihydroxy ethylene urea (50% w./w.) were diluted with water and added to 200 cc. 12 N sulphuric acid, the solution was then made up to 500 cc. with water. This solution had an acid normality of 5.4 N.

A tubular knitted cotton fabric was padded in this solution and kept, wet with solution, for 5 hours at 20 C. During this period the fabric was maintained stretched in the length by 1% and in the width by 25%. The fabric was then neutralised in sodium carbonate solution, rinsed well in water and dried at its original dimensions. The change in dimensions after washing for 10 minutes at the boil in 0.2% soap solution were:

Shrinkage (percent) Length Width Untreated Treated row 1 A negative sign signifies extension.

Example 24 fabric was creased. Fibres from the treated fabric were insoluble in cuprammonium hydroxide solution.

Example 25 A length of yarn-dyed cotton gabardine was treated as in Example 22. After the treatment the fabric was adjustedtooriginal dimensions'within 1% 13'' The treated fabric was found to have good dimensional stability to washing when tested according to the British Standards method BS 1118.

Shrinkage (percent) Warp Weft Untreated 11. 9 2. Treated 1. 75 0. 75

Specimens of treated fabric were shown to give satisfactory water repellency when proofed with waxes, Slllcones, or fatty chain pyridinium compounds.

Example 26 Example 27 A reaction mixture of dicyandiamide and formaldehyde in molecular ratio 1132 was prepared by heating 42 g. dicyandiarnide with 121 cc. formaldehyde solution (40% w./v.) under reflux for 10 minutes at 100 C. The solution was cooled and diluted with water to 350 cc. 40 g. of the solution were added to 40 cc. 12 N sulphuric acid and the volume made up to 100 cc. with water for impregnation.

Specimens of mercerised cotton poplin fabric were padded through this acid solution, wrapped to prevent the fabric drying, stored for 19 hours at 20 C., neutralised in sodium carbonate solution, well rinsed in water and dried. The treated fabric had improved wet crease shedding properties compared with the untreated fabric. Fibres from the treated fabric were insoluble in cuprammonium hydroxide solution.

Example 28 20 g. of a solution of dimethylol dihydroxy ethylene urea, (50%) were diluted with water and added to an aqueous solution which contained 50 g. trichloracetic acid. The total volume of the solution was made up to 100 cc. with water. Specimens of mercerised cotton fabric were padded in the solution, rolled on tubes, wrapped to prevent the fabric drying and stored for 21 hours at 20 C. The fabric was then neutralised in sodium carbonate solution, rinsed Well in water and dried. The treated fabric had improved wet crease shedding properties compared with the untreated fabric and was insoluble in cuprammonium hydroxide solution.

Other specimens of the cotton fabric were treated as above except that the solution used contained 9 g. trimethylol melamine instead of the 20 g. dimethylol dihydroxy ethylene urea solution.

The treated fabric was found to be insoluble in cuprammonium hydroxide solution.

Example 29 A reaction product of urea, formaldehyde and glyoxal in molecular proportion 1:1:1 was prepared by the procedure given in Example 14. The product of the reaction was applied to specimens of the cotton poplin fabric as in Example 14.

The treated fabric was found to have improved wet crease shedding properties when compared with untreated fabric, and was insoluble in cuprammonium hydroxide solution.

1 4 Example 30 Regenerated cellulose film described as non moisture proof plain transparent wrapping 300 substance manufactured by British Cellophane Ltd., was treated with an aqueous solution of the dimethylol dihydroxy ethylene urea and sulphuric acid as in Example 6. The treated cellulose film material was found to be insoluble in cuprammonium hydroxide solution whereas the untreated material was soluble in such solution.

Example 31 20 g. of, a solution of dimethylol (1,3-propylene) urea (50% W./w.) were diluted with water and added to 40 cc. 12 N sulphuric acid. The volume of solution was then made up to 100 cc. with water. Specimens of cotton poplin fabric were padded in the solution, and treated by the procedure of Example 14. Fibres from the treated fabric were found to be insoluble in cuprammonium hydroxide solution.

Example 32 A reaction mixture was prepared by adding to 40 cc. 13 N sulphuric acid, 8.5 cc. formaldehyde solution (40% w./v.), 8.7 cc. glyoxal solution (37% w./v.) and 3.4 g. urea. The mixture was made up to 100 cc. with water and stirred until the urea had dissolved. The reaction mixture was allowed to stand for 24 hours at room temperature. Specimens of mercerised cotton poplin fabric were padded in the solution and treated by the procedure of Example 14. The treated fabric had good wet crease shedding properties, and the fibres were insoluble in cuprammonium hydroxide.

Example 33 A reaction mixture of adipamide and formaldehyde in molecular ratio 1:2 was prepared by heating 144 g. adipamide with 150 cc. formaldehyde solution (40% w./v.) and 250 cc. of water under reflux for 10 minutes at 100 C.

26 g. of the solution were added to 40 cc. 13 N sulphuric acid and the volume made up to 100 cc. with water.

Specimens of mercerised cotton poplin fabric were padded in this acid solution, and treated according to the method of Example 27.

The treated fabric had improved wet crease shedding properties and was insoluble in cuprammonium hydroxide solution.

Example 34 Specimens of mercerised cotton poplin fabric were treated with an acid solution of dimethylol dihydroxy ethylene urea as in Example 6.

The specimens were then given a post-resination treatment by padding in a solution containing:

10 g. dimethylol tetrahydro-S-ethyl-s-triazinone 1 g. zinc nitrate hexahydrate 0.05 g. acetic acid per 100 cc. of solution drying and curing for 3 minutes at 150 C. The specimens were then washed for 2 minutes at 60 C. in a solution of 0.1% sodium carbonate and 0.2% sodium perborate, and dried.

The treated fabric had good wet and dry crease recovery properties.

Example 35 A reaction mixture of urethane, formaldehyde and glyoxal in molecular ratio 1:2:1 was prepared as follows.

52 cc. glyoxal solution (37% w./v.) Were added to 50 cc. formaldehyde solution (40% w./v.) and the pH adjusted to 8.

27 g. urethane were added and the mixture heated under reflux for minutes at 80 C.

50 g. of the product were added to 40 cc. 13 N sulphuric acid and the volume made up to cc. with water. Specimens of a mercerised cotton poplin fabric were padded in this solution and treated by the procedure of Example 14.

The treated fabric had improved wet crease shedding properties and was insoluble in cuprammonium hydroxide solution.

Example 36 Specimens of plain weave unmercerised cotton fabric were damped with water and calendered at 370 F. between a heated metal roller and compressed paper bowl. The specimens were then treated with a solution of dimethylol dihydroxy ethylene urea and sulphuric acid as in Example 6.

A lustrous, glazed finish was obtained which was resistant to washing in a boiling soap solution.

Example 37 450 cc. concentrated sulphuric acid are added to 350 cc. water with cooling, and 200 g. of an aqueous solution of dimethylol dihydroxy ethylene urea (50%) were added with stirring. A length of cotton fabric was padded at open width in the solution maintained at 30 C. and the wet fabric was passed in a continuous fashion over rollers for 90 seconds before entering a neutralising solution containing sodium carbonate. The fabric was then well rinsed with water, still in open width, and finally dried.

The treated fabric possessed improved wet crease shedding properties.

Example 38 A kraft paper was passed through a 15 N solution of sulphuric acid which contained 10 g. dimethylol dihydroxy ethylene urea for every 100 cc. of solution, for a period of 2 minutes at C. The paper was passed into a rinsing bath of water and neutralised. After drying the treated paper showed an improvement in wet bursting strength.

Example 39 20 g. of a solution of dimethylol dihydroxy ethylene urea (50%) were added to 40 cc. 13 N sulphuric acid, and 2 g. sodium carboxy methyl cellulose swollen in a small amount of water were added with stirring. The volume was made up to 100 cc. A cotton poplin was padded in the solution, batched and wet stored for 3 hours at 20 C. before neutralising and rinsing well in water. A firm fabric with extremely good wet crease recovery was obtained. The firmness was not removed on washing at the boil.

Similar results were obtained when the sodium carboxy methyl cellulose was applied first instead of in the mixture as above.

Example 40 A plain cotton interlining fabric was padded in polyvinyl alcohol solution (l%) and dried. The dry fabric was then passed into an acid solution of dimethylol dihydroxy ethylene urea and treated by the procedure of Example 6. The treated fabric had a crisp handle which was maintained after washing in a boiling soap solution and which had improved wet crease shedding properties. Similar results were obtained when the fabric was pretreated in a starch solution (1%) instead of in polyvinyl alcohol solution.

Example 41 What is claimed is:

1. A process for the treatment of material comprising a cellulosic substance selected from the group consisting of cellulose and cellulose derivative which still retain replaceable hydrogen atoms, consisting essentially of contacting said material with an aqueous liquor comprising (1) at least one methlolated nitrogen compound and (2) an acid, swelling the material with said liquor, maintaining the material in the wet swollen condition while permitting the reaction to take place between the contents of the liquor and said material so that chemical modification of the cellulose molecules occurs causing the cellulose to become substantially insoluble in cuprammonium hydroxide solution while maintaining swellability in water, removing acidic matter and unreacted reagents from the material and drying said fabric.

2. A process according to claim 1 wherein the methylolated nitrogen compound is a methylolated cyclic urea and said cyclic urea contains at least one hydroxy group.

3. A process according to claim 1 in which the methylolated nitrogen compound is a polymethylol ethylene urea.

4. A process according to claim 1 in which the methylolated nitrogen compound is the dimethylol derivative of dihydroxy ethylene urea.

5. A process according to claim 1 in which the acid is a mineral acid.

6. A process according to claim 5 performed at about room temperature.

7. A process according to claim 1 in which the acid is sulfuric acid and the acid concentration in the treatment liquor is from 4 N to 10 N acid strength.

8. A process according to claim 1 in which the dura-' tion of the aqueous liquor treatment is from 1 minute to 24 hours.

9. A process according to claim 1 carried out at an elevated temperature.

10. process according to claim 1 wherein the material is held in a stretched condition during the aqueous liquor treatment.

11. A process according to claim 1 in which the material to be treated is impregnated with the aqueous liquor and then batched and allowed to stand, while preventing drying out, for a length of time sufficient for the desired reaction to have taken place.

12. A process according to claim 1 carried out continuously by passing the material through a bath of the aqueous liquor, carrying it forward from the bath in a wet swollen state while reaction takes place, then passing it through a neutralizing solution and rinsing water and finally through a drying stage.

13. A process according to claim 1 applied to material previously subjected to a finishing operation.

14. A process for the treatment of material comprising a cellulosic substance selected from the group consisting of cellulose and cellulose derivatives which still retain replaceable hydrogen atoms, consisting essentially of contacting said material with an aqueous liquor comprising (1) at least one nitrogen compound from the class consisting of dimethylol ethylene urea, dimethylol dihydroxy ethylene urea, tetramethylol acetylene diurea, dimethylol tetrahydro-S-ethyl-s-triazinone, dimethylol-1,3-propylene urea, dimethylol adipamide, methylolated urethane and dihydroxy ethylene urea and (2) an acid, swelling the material with said liquor, maintaining the material in the wet swollen condition while permitting reaction to take place between the contents of the liquor and said material so that chemical modification of the cellulose molecules occurs causing the cellulose to become substantially insoluble in cuprammonium hydroxide solution while maintaining swellability in water, and thereafter, before drying, removing acidic matter and unreacted reagents from the material.

(References on following page) References Cited by the Examiner UNITED STATES PATENTS Ellis 8--116.3 X Wolf et a1. 8116.3 X Thackston 8116.3 X Burks 8116.3 X

OTHER REFERENCES Reid et al.: Textile Industries, November 1958, pp. 1-10.

5 NORMAN G. TORCHIN, Primary Examiner.

FRANK CACCIAPAGLIA, JR., ABRAHAM WINKEL- STEIN, Examiners. 

1. A PROCESS FOR THE TREATMENT OF MATERIAL COMPRISING A CELLULOSIC SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF CELLULOSE AND CELLULOSE DERIVATIVE WHICH STILL RETAIN REPLACEABLE HYDROGEN ATOMS, CONSISTING ESSENTIALLY OF CONTACTING SAID MATERIAL WITH AN AQUEOUS LIQUOR COMPRISING (1) AT LEAST ONE METHOLATED NITROGEN COMPOUND AND (2) AND ACID, SWELLING THE MATERIAL WITH SAID LIQUOR, MAINTAINING THE MATERIAL IN THE WET SWOLLEN CONDITION WHILE PERMITTING THE REACTION TO TAKE PLACE BETWEEN THE CONTENTS OF THE LIQUOR AND SAID MATERIAL SO THAT CHEMICAL MODIFICATION OF THE CELLULOSE MOLEULES OCCURS CAUSING THE CELLULOSE TO BECOME SUBSTANTIALLY INSOLUBLE IN CUPRAMMONIUM HYDROXIDE SOLUTIN WHILE MAINTAINING SWELLABILITY IN WATER, REMOVING ACIDIC MATTER AND UNREACTED REAGENTS FROM THE MATERIAL AND DRYING SAID FABRIC. 